1kbar、800℃下REE在富磷过铝质熔体/流体相间分配的实验研究

利用"RQV-快速内冷淬火"(或称之为"外加热冷封式")高温高压实验装置,实验研究了1kbar、800℃条件下12个REE+Y在富磷过铝质熔体/含水流体相间的分配,并利用EMP、LA-ICPMS和ICP-MS分析技术分别测定了实验初始物、实验产物玻璃中主要化学组成以及熔体相和流体相中REE含量。实验结果表明,REE元素(La,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu)在流体/熔体相间的分配系数(Dfluid/melt)在(0.1～19.9)×10-4范围,DfYluid/melt在(0.2～7.8)×10-4范围,指示REE和Y强烈趋向于在熔体中富集。REE在流体/熔体相间的分配系数(Dfluid/melt)与体系中P2O5含量变化呈近抛物线状分布,其最大值对应于残余熔体中w(P2O5)为1.44%处。REE在流体/熔体相间的分配系数(Dfluid/melt)随REE的原子序数增大而逐渐降低,构成右倾的平滑曲线,总体上显示出DLREE>DMREE>DHREE的趋势。Y与Ho在流体/熔体相间分配系数的比值(DY/DHo)约为1(0.91～1.28),不随体系中P2O5变化而变化的特征。上述特征表明熔体-流体作用不会导致Y-Ho及REE间的分异,因此,可推断熔体-流体作用过程不可能是过铝质岩浆体系中产生稀土"四重效应"机制。     

100MPa、800℃下Mo和W在流体／花岗质熔体相间分配的实验研究

利用“RQV-快速内冷淬火”（外加热冷封式）高温高压实验装置,在100MPa、800℃条件下,以东秦岭地区出露的高钾钙碱性岩浆岩（合峪花岗岩）为实验初始物,实验研究了Mo和W在花岗岩-H2O、花岗岩-NaCl（KCl）-H2O及花岗岩-NaF-H2O体系流体／熔体相间的分配行为。实验结果表明,Mo比W更倾向于分配进入流体相（DMo^流体/溶体〉〉DW^流体/溶体）,相对于纯水体系而言,流体介质中Cl和F的存在均有利于Mo和W向流体相迁移富集,随体系内Cl含量的不断增高,Mo和W的分配系数呈线性增大趋势,而在天然花岗岩可能含有的F含量范围之内,F含量的增高将阻碍Mo、W向流体相迁移,流体介质中Na／K（摩尔比）的变化对Mo和W的分配系数没有明显影响,表明体系碱质（Na或K）类型不是Mo和W在流体／熔体相间分配的主要影响因素。     

钼在花岗质熔体相和流体相间的分配实验

在750—850℃、(1.5—2.5)×10~8Pa条件下,以玻璃或凝胶作为初始样品,研究了钼在流体相和花岗质熔体相间的分配系数,同时还测定了铁、钙、钾的分配系数。解释了斑岩型钼矿床的可能成矿作用。     

熔体-流体作用是过铝质岩浆体系产生稀土"四重效应"的机制?——REE在流体/熔体相分配的实验研究

过铝质岩浆体系以存在稀土"四重效应"和等价不相容元素对显著分异(Y-Ho、Nb-Ta、Zr-Hf)为特征[1-2].对于其形成机理,目前普遍认为是岩浆-热液过渡阶段的产物,是熔体与含氟流体作用的结果,即REE在流体-熔体相之间分异所致[3-6].     

Sn、Fe、W、Pb和Zn在花岗岩熔体及共存流体相之间的分配实验研究:850℃和400 MPa

本实验的目的在于了解花岗岩岩浆演化过程中,F/Cl在介质中的不同比值对Sn、Fe、W、Pb和Zn等元素从岩浆熔体进入超临界水热流体相中的影响.采用天然花岗岩为原始样品,实验在大型内加热装置容器(Harwood Engineering Co.Inc.)中进行.实验条件为850℃,400 MPa,fo2=2.1×10-13(NNO),恒温约120～128 h.固/液比值≈1,固样质量约250 mg,Ar为压力介质.实验结果显示,介质中F/Cl比值变化对W的分配系数影响不大.而其他元素均随Cl浓度增高,分配系数增大,并有以下顺序:DV/LZn＞DV/LPB＞DV/LFe＞DV/LSn.通常认为四价Sn较为稳定并与F关系密切,而本实验显示,二价Sn可能较为稳定并与Cl关系密切.在快速淬火过程中,沉淀在金管壁上的玻璃碎屑富集了较多的成矿元素,且观察到玻璃包裹体及盐类包裹体.     

花岗岩+P2O5-H2O体系中W、Sn、Be、Nb、Ta在流体/熔体间分配的实验研究

实验研究了W、Sn、Be、Nb、Ta在不同压力(150 MPa、100MPa和50 MPa)、温度(850℃和800℃)条件下,于水饱和含P过铝质岩浆体系(P2O5分别为0.32%、1.98%、4.91%和7.78%)中流体-熔体间的分配.研究结果显示,W、Sn、Be、Nb、Ta在流体/熔体相间的分配系数Di＜0.1,表明它们强烈分配进入熔体相.W、Nb、Ta在流体/熔体相间的分配显示压力相关性随压力降低而降低.     

富P过铝质岩浆体系的研究现状及存在的问题

高度演化的富P过铝质岩浆体系,具有鲜明的、不同于其他体系的地球化学行为.富P过铝质熔体以富P,高ASI,贫Fe、Mg、Ca,强烈亏损REE、Th、Y以及具有W、Sn、Nb、Ta等金属的矿化为特征.富P过铝质岩浆体系中的碱性长石为富P长石,长石中P可以有效地指示过铝质岩浆体系的演化历程;在岩浆演化的晚期,P与Li具强的亲和性,形成锂辉石-磷铝锂石-羟磷铝锂石的组合.已有的实验研究揭示,P能降低简单花岗岩的液相线和固相线温度、粘度以及增加H2O在熔体中的溶解度.然而,这一体系还存在许多问题亟待研究,P能否促进过铝质岩浆的液态不混溶,能否促使等价不相容元素在过铝质岩浆演化过程中的分异,是否在稀有金属成矿过程中起作用等都是值得关注的问题.     

锡在流体和花岗质硅酸盐熔体间分配行为的实验研究

锡的成矿与花岗岩有着密切关系。为深入了解不同的岩浆组成及流体变化对锡分配行为的影响,以不同化学组成的凝胶和不同的流体分别作为初始固液相,进行了锡在流体与花岗质熔体间的分配行为实验研究。实验温度为850℃,压力为100 MPa。结果显示,当液相为0.1 mol/L的HCl时,熔体组成的变化对锡的分配行为有着明显的影响,锡在流熔体间的分配系数DSn随熔体中碱质(Na2O K2O)含量、钠钾(Na/K)和碱铝(AlK/Al)摩尔比的增加而减小;在固相(富钾过碱质熔体)不变的前提下,DSn随流体相中HCl浓度的增加而增大,而流体相中HF及K 、Na 浓度的改变对DSn影响不大;流体Cl-浓度和酸度升高有利于锡分配进入流体相。     

钨在水流体和硅酸盐熔体相间分配的实验研究

在800℃,15×10~7Pa条件下,以天然花岗岩为试料,对钨在水流体和花岗岩熔体相间的分配进行了实验研究。实验中主要考虑了挥发分和温度对分配系数的影响。     

The Partitioning of Tungsten bwtween Aqueous Fluids and Silicate Melts

An experimental study has been carried out to determine the partition coefficients of tungsten between aqueous fluids and granitic melts at 800 °C and 1.5 kb with natural granite as the starting material. The effects of the solutions on the partition coefficients of tungsten show a sequence of P > CO ₃ ²⁻ > B > H₂O. The effects are limited (generallyK _D < 0.3) and the tungsten shows a preferential trend toward the melt over the aqueous fluid. The value ofK _D increases with increasing concentration of phosphorus; theK _D increases first and then reduces with the concentration of CO ₃ ²⁻ when temperature decreases, theK _D between the solution of CO ₃ ²⁻ and the silicate melt increases, and that between the solution of B₄O ₇ ²⁻ and the silicate melt decreases. The partition coefficients of phosphorus and sodium between fluids and silicate melts have been calculated from the concentrations of the elements in the melts. TheK _D value for phosphorus is 0.38 and that for sodium is 0.56. Evidence shows that the elements tend to become richer and richer in the melts.     

An experimental determination of W,Nb, and Ta partition coefficients between P-rich peraluminous granitic melt and coexisting aqueous fluid

Acta Geochimica - The partition coefficients of W, Nb, and Ta between the P-rich peraluminous granitic melt and the coexisting aqueous fluid were determined at 800–850&nbsp;°C and...     

硼在共存水蒸气-富硼熔体之间分配的实验研究及其地质意义

硼作为一种常用的地球化学指示剂和示踪剂,对研究俯冲带岩石学过程、岩浆-热液分异作用、火山活动以及稀有元素、铜、金的成矿机制具有重要意义。硼具有高水溶性和挥发性,它在气体中的分配、迁移能力和存在形式有助于理解含硼矿物的形成条件、流体化学组成的演化趋势、硼同位素的分馏效应和成矿金属的富集机理。本文在200-350℃、0.19-3.43 MPa条件下实验研究了B2O3-H2O体系中硼在共存水蒸气和富硼熔体（液体）之间的分配,平衡时气相中的B2O3含量为1.06%-32.35%。200℃、250℃、300℃和350℃时硼在气体-熔体之间的表观分配系数分别为0.035、0.042、0.20和0.33,即随温度上升,硼在含水气相中的分配和迁移能力增强。含水的富 B 熔体与硼酸稀溶液体系的气体-液体分配系数变化不大,表明B2O3-H2O±NaCl 体系中硼的气-液分配能力受液体或熔体中硼含量的影响较小,而主要与温度有关。经热力学分析,350℃、0.19-1.74 MPa条件下水蒸气中的气态硼物种可能为H3BO3和HBO2,可以预计随水蒸气压力的升高, H2O的配位数将会增大, H3BO3或其他可能的气态物种H3BO3·H2O会变得更为重要。某些火山活动区可见天然硼酸结壳（升华壳）的形成,灼热和干燥的火山岩石表面有利于硼酸从气相中凝析和沉淀。本实验结果表明,某些富硼酸的火山喷气孔气体的形成可能与地下高温火山岩浆（岩体）中存在因液态不混溶作用或晚期出溶作用产生的含水富硼的残余熔体或流体有关,熔体的去气作用或流体的减压相分离导致含水气相的产生,硼则随之大量分配至含水气体中并喷出地表。     

Partitioning of F between aqueous fluids and albite granite melt and its petrogenetic and metallogenetic significance

The fluid/melt partitioning experiments on fluorine were carried out in the system albite-H₂O-HF atP = 100 MPa, 770°C ≤T≤800°C: and wt = 2% −6% conditions. The concentrations of fluorine in quenched glasses (melt) were determined by electron microprobe and those of fluorine in the coexisting aqueous fluid were calculated by the method of mass balance. The result shows that the fluorine was concentrated in granitic melt relative to the coexisting fluid. The partition coefficient D_F(wt _F ^F1 /wt _F ^Mt ) ranges from 0.35 to 0.89. It increases with increasing fluorine content in the system. This means that there is not just one single value of partition coefficient for fluorine in the granitic melt-fluid system. The partitioning behavior of fluorine in this system depends critically on fluorine and proton (H⁺) concentrations. Our data suggest that F-rich granitic melts exist in nature and that fluorine may not be an important complexing agent of metal elements in F-bearing fluids. The project was financially supported by both the National Natural Science Foundation of China (No. 49603048) and the State Key Laboratory of Mineral Deposit Research, Nanjing University.     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

Experimental study of partitioning of tantalum,niobium, manganese,and fluorine between aqueous fluoride fluid and granitic and alkaline melts

This study presents a new set of quantitative experimental data on the partitioning of Ta, Nb, Mn, and F between aqueous F-bearing fluid and water-saturated, Li- and F-rich haplogranite melts with varying alumina/alkali content at T = 650–850 °C and P = 100 MPa. The starting homogeneous glasses were preliminary obtained by melting of three gel mixtures of K₂O-Na₂O-Al₂O₃-SiO₂ composition with a variable Al₂O₃/(Na₂O+K₂O) ratio, ranging from 0.64 (alkaline) and 1.1 (near-normal) to 1.7 (alumina-rich). Ta, Nb, and Mn were originally present in glass only, whereas F was load in both the glass and the solution. The solutionto-glass weight ratio was 1.5–3.0. The compositions of quenched glass were measured by an electronic microprobe, and those of the aqueous solution, with the ICP-MS and ICP-AES methods. The F concentration in the quenched solution was calculated from the mass balance. Under experimental conditions the partition coefficients of Ta, Nb, and Mn between the fluid and the granitic melt (weight ratio ^fluid C _Ta/^melt C _Ta = ^fluid/melt D _Ta) are shown to be extremely low (0.001–0.008 for Ta, 0.001–0.022 for Nb, and 0.002–0.010 for Mn); thus, these metals partition preferentially into the melt. The coefficients ^fluid/melt D _Ta and ^fluid/melt D _Nb generally increase either with increasing alumina ratio A/NKM in the glass composition, or with rising temperature. The experiments also demonstrated that F preferentially concentrates in the melt; and the partition coefficients of F are below 1, being within the range of 0.1–0.7.

     

煤层应力敏感性及其对压裂液滤失的影响

压裂液滤失系数是压裂设计中非常重要的参数。由于煤层中的渗透率、孔隙度等物性对应力极为敏感,在对煤层进行压裂设计时,若直接用试井和测井测得的渗透率和孔隙度值代入滤失系数的计算公式,算出的结果可能与实际情况严重不符。通过实验室内不断改变围压的方式来模拟煤储层上覆压力的变化情况,建立了某盆地煤层应力与渗透率之间的关系,并在考虑煤层物性应力敏感性的情况下,探讨了煤层压裂液综合滤失系数的计算方法。结果发现,压裂液综合滤失系数及岩心渗透率与净围压的关系均符合指数递减规律。另外,通过对动态渗透率的拟合,使得到的综合滤失系数远远大于未考虑应力情况下的综合滤失系数,这样能更准确地反映实际情况。     

变质玄武岩体系相平衡及矿物 熔体微量元素分配：限定TTG/埃达克岩形成条件和大陆壳生长模型

埃达克质岩石是高Na、Al和Sr、低Y和HREE以及Nb、Ta亏损的钠质花岗质岩石,奥长花岗岩-英云闪长岩-花岗闪长岩(TTG)是早期(太古宙)大陆壳主要组分,成分与埃达克质岩石相似,这些成分独特的岩石总体上认为是俯冲洋壳、下地壳和拆沉的下地壳中变质玄武岩部分熔融的产物。文中综述我们近年来在变质玄武岩体系相平衡和矿物-熔体微量元素分配实验研究成果:相平衡实验和熔体微量元素特征研究表明,变质玄武岩部分熔融过程中金红石是导致TTG/埃达克岩浆Nb、Ta亏损的必要残留矿物,从而否定了前人“TTG由无金红石的角闪岩熔融产生”的观点;证实金红石仅仅在压力1.5GPa以上才能稳定存在,从而限定TTG/埃达克岩熔体必定产生在大约50km以上,表明TTG/埃达克岩是在相对较深的含金红石榴辉岩相条件下熔融产生的。矿物(石榴子石、角闪石,单斜辉石和金红石)-熔体微量元素分配系数测定和部分熔融模拟结果进一步限定俯冲洋壳和下地壳起源的TTG/埃达克岩浆由含金红石角闪榴辉岩熔融产生,而拆沉下地壳起源的埃达克岩浆的产生要求软流圈地幔高温,由无水或含有少量含水矿物的榴辉岩熔融产生。